Thiazoline carbamoyl-oximes

ABSTRACT

Carbamoyl-oxime compound of the formula ##STR1## wherein A, R 3 , R 4  and R 5  are as hereinafter set forth, a process for their preparation, pesticidal compositions containing one or more of these compounds as the active ingredient, methods of use of such compositions for the control of pests, particularly insects, mites, nematodes and molluscs, and intermediates for the production of such compounds are described.

DETAILED DESCRIPTION OF THE INVENTION

This invention is directed to carbamoyl oximes of the formula ##STR2##wherein A is a group (a) or (b) ##STR3## R¹ and R² are hydrogen, loweralkyl or cycloalkyl, or together with the carbon atom to which they areattached a 4- to 6-membered, saturated hydrocarbon ring,

R³ is hydrogen, lower alkyl or cycloalkyl,

R⁴ is hydrogen

and

R⁵ is lower alkyl, lower alkenyl or cycloalkyl,

or

R⁴ is lower alkyl

and

R⁵ is lower alkyl, lower alkylcarbonyl, tri(lower alkyl)silyl or a group(c)

    --S.sub.m --R.sup.6                                        (c)

R⁶ is alkyl, lower haloalkyl; phenyl, phenyl substituted with halogen,lower alkyl and/or trifluoromethyl; or a group (d) or (e)

    --NR.sup.7 R.sup.8                                         (d) ##STR4## R.sup.7 and R.sup.8 are lower alkyl or lower haloalkyl, or together with the nitrogen atom to which they are attached a piperidino or morpholino group,

R⁹ is lower alkyl

and

m is 1 or 2.

The compounds of formula I are useful for the control of pests and areespecially suitable for the control of insects, mites, nematodes andmolluscs. Accordingly, the invention is also directed to pesticidalcompositions which contain one or more of the compounds of formula I asthe active ingredient.

This invention is also directed to processes for the preparation ofthese pesticidal compositions as well as methods for their use.

As used herein the term "lower alkyl" denotes both straight-chain andbranched-chain hydrocarbon groups containing from 1 to 4 carbons such asmethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert.-butyl.This connotation also applies to those groups containing lower alkylmoieties such as lower alkylcarbonyl and lower haloalkyl. The term"lower alkenyl" denotes straight-chain and branched-chain unsaturatedhydrocarbon groups containing from 2 to 5 carbon atoms such as vinyl,allyl, butenyl, pentenyl, and the like. The term "halogen" includesfluorine, chlorine, bromine and iodine. The term "cycloalkyl" includescyclic groups of from 3 to 6 carbon atoms such as cyclopropyl,cyclobutyl, cyclopentyl and cyclohexyl. When two or more substituentsare present in a substituted phenyl group, the substituents can be thesame or different.

The invention also encompasses the syn- and anti-forms of the compoundsof formula I, of which the syn(Z)-forms are preferred. Since asymmetriccarbon atoms can be present, optical antipodes exist in such cases. Bythe presence of the double bond in the compounds of formula I wherein R⁵denotes lower alkenyl, geometric isomers additionally occur for suchcompounds. Formula I is accordingly intended to include all of thesepossible isomeric forms.

Compounds of formula I in which R¹ and R² is lower alkyl such as methylor ethyl, and particularly methyl are preferred. Moreover, the totalnumber of carbon atoms in the substituents R¹ and R² of these compoundspreferably does not exceed 4.

Also preferred are compounds of formula I in which R¹ and R² togetherwith the carbon atom to which they are attached is a 4- to 6-membered,saturated hydrocarbon ring, particularly a 5- to 6-membered ring.

Compounds of formula I in which R¹ and R² each denote hydrogen or loweralkyl are preferred.

Compounds of formula I in which A is group (a), and R³ is lower alkylsuch as methyl are preferred.

Also preferred are compounds of formula I in which A is the group (b),and R³ is lower alkyl, particularly isopropyl.

Compounds of formula I in which R⁴ is lower alkyl, particularly methyl,are preferred.

Compounds of formula I are preferred where R⁵ is lower alkyl, loweralkenyl, cycloalkyl, lower alkylcarbonyl or tri(lower alkyl)silyl,particularly methyl, allyl, cyclopropyl, acetyl, or trimethylsilyl ortri(tert.-butyl)silyl respectively.

Also preferred are compounds of formula I where R⁵ is the group (c), andR⁶ is alkyl containing up to 8 carbon atoms.

Also preferred are compounds of formula I where R⁶ in group (c) is lowerhaloalkyl, particularly trichloromethyl, dichlorofluoromethyl ortrifluoromethyl.

Compounds of formula I in which R⁵ is lower alkyl, particularly methyl,and R⁴ is hydrogen are preferred.

Especially preferred compounds of formula I are:

5-Oxo-2,2,4-trimethyl-3-thiazoline O-(methylcarbamoyl) oxime and

2-oxo-5,6-dihydro-3-isopropyl-2H-1,4-thiazine O-(methylcarbamoyl) oxime.

Further examples of compounds of formula I are:

5-Oxo-4-methyl-3-thiazoline O-(methylcarbamoyl) oxime,

5-Oxo-2-cyclopropyl-2,4-dimethyl-3-thiazoline O-(methylcarbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazoline O-(allylcarbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazoline O-(cyclopropylcarbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazoline O-(N-acetyl-N-methylcarbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-methyl-N-trimethylsilylcarbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-methyl-N-(methylsulphenyl)carbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-methyl-N-(methylthiosulphenyl)carbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-isopropylthiosulphenyl-N-methylcarbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-tert.-butylthiosulphenyl)-N-methylcarbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-methyl-N-(n-octylthiosulphenyl)carbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-trichloromethylsulphenyl-N-methylcarbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-dichlorofluoromethylsulphenyl-N-methylcarbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-trifluoromethylsulphenyl-N-methylcarbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-[(4-chlorophenyl)sulphenyl]-N-methylcarbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-methyl-N-[(2-methylphenyl)sulphenyl]carbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-methyl-N-[(4-methylphenyl)sulphenyl]carbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-[(3,4-dimethylphenyl)sulphenyl]-N-methylcarbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-methyl-N-[(3-trifluoromethylphenyl)sulphenyl]carbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-[(4-tert.-butylphenyl)thiosulphenyl]-N-methylcarbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-dimethylaminosulphenyl-N-methylcarbamoyl) oxime,

5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-di(2-chloroethyl)aminosulphenyl-N-methylcarbamoyl) oxime and

N,N'-bis-(2,2,4-trimethyl-3-thiazoline-5-O-(methylcarbamoyl)oximino)-disulphide.

The compounds of this invention are prepared by the processes describedbelow.

Procedure A

An oxime of the formula ##STR5## wherein A and R³ are as definedearlier, is reacted with an isocyanate of the formula

    R.sup.5 --N═C═O                                    III

wherein R⁵ is as defined earlier,

conveniently in the presence of a diluent and, optionally, in thepresence of a catalyst.

Procedure A affords compounds of formula I wherein R⁴ is hydrogen, andR⁵ is lower alkyl, lower alkenyl or cycloalkyl.

Diluents for the reaction of Procedure A include inert organic solvents.Preferred solvents are ethers and ether-like compounds such as1,2-dimethoxyethane, tetrahydrofuran and dioxan; ketones such as diethylketone, particularly acetone and methyl ethyl ketone; nitriles such aspropionitrile, particularly acetonitrile; formamides such asdimethylformamide; and halogenated hydrocarbons such as methylenechloride, carbon tetrachloride and chloroform.

Preferred catalysts are tertiary bases such as triethylamine, pyridineand 1,4-diazabicyclo[2.2.2]octane; and organic tin compounds such asdibutyl tin diacetate.

The reaction temperatures can vary over a wide range. In general, thereaction is carried out at a temperature between 0° C. and 100° C., and,preferably between 20° C. and 50° C. When a solvent is present, thereaction is conveniently carried out at the boiling point of the solventused.

The reaction is preferably carried out using an excess of isocyanate offormula III. The compounds of formula I wherein R⁴ represents hydrogenare isolated by distilling the solvent and working up the residue bystandard procedures.

Precedure B

An oxime of formula II, as defined earlier, is reacted with a carbamoylhalide of the formula ##STR6## wherein R⁴ and R⁵ are as defined earlier,and X is a halogen atom,

conveniently in the presence of a diluent and an acid-binding agent.

Diluents for the reaction of Procedure B include inert organic solvents.Preferred solvents are those mentioned for Procedure A above.

The reaction is conveniently carried out in the presence of anacid-binding agent. While any inorganic and organic acid-binding agentscan be used, the preferred acid-binding agents are sodium hydride;alkali carbonates such as sodium carbonate, potassium carbonate andsodium bicarbonate; lower tertiary alkylamines, cycloalkylamines andarylalkylamines such as triethylamine and dimethylbenzylcyclohexylamine;pyridine and diazabicyclooctane.

The reaction temperatures can vary over a wide range. In general, thereaction is carried out at a temperature between 0° C. and 100° C., and,preferably, between 0° C. and 40° C.

The reaction is preferably carried out using 1 to 2 mol of carbamoylhalide of formula IV for each mol of the oxime of formula II. A slightexcess of acid-binding agent (up to ca.30 weight percent) isadvantageous. The isolation of compounds of formula I is carried outusing standard procedures.

Procedure C

An oxime of formula II, as defined above, is reacted with phosgene andsubsequently an amine of the formula ##STR7## wherein R⁴ and R⁵ are asdefined above, conveniently in the presence of a diluent and anacid-binding agent.

Diluents for the reaction of Procedure C include inert organic solvents.Preferred solvents are ethers and ether-like compounds such as1,2-dimethoxyethane, tetrahydrofuran and dioxan; nitriles such asacetonitrile; formamides such as dimethylformamide; and hydrocarbonssuch as toluene.

The reaction is conveniently carried out in the presence of anacid-binding agent. While any inorganic and organic acid-binding agentscan be used, the preferred acid-binding agents are those mentioned forProcedure B above.

The reaction temperatures can vary over a wide range. In general, thereaction is carried out at a temperature between 0° C. and 100° C., and,preferably between 0° C. and 40° C.

The reaction procedure is conveniently carried out as a one-pot process.Phosgene is reacted with the oxime of formula II and then the amine offormula V is added to the reaction mixture. It has been found to beadvantageous to employ for 1 mol of oxime of formula II 1 to 1.5 mol ofphosgene and 1 to 1.5 mol of amine of formula V. Further, a slightexcess of acid-binding agent, e.g. up to about 30 weight percent, ispreferably used. The isolation of the compounds of formula I is carriedout using standard procedures.

Procedure D

A carbamoyl oxime of the formula ##STR8## wherein A and R³ are asdefined earlier, and R¹⁰ is lower alkyl, which may be obtained accordingto one of the above process variants, is reacted with a sulphenylchloride of the formula

    Cl--S.sub.m --R.sup.11                                     VI

wherein m is 1 or 2, and R¹¹ is as defined earlier for R⁶ or chlorine,

conveniently in the presence of a diluent and an acid-binding agent.

Procedure D affords compounds of formula I wherein R⁴ is lower alkyl,and R⁵ is a group (c).

The diluents and acid-binding agents utilized in this reaction are thosementioned above in connection with Procedures A and B. The reaction isgenerally carried out at a temperature between 0° C. and 100° C., and,preferably, between 0° C. and 50° C.

Where a sulphenyl chloride of formula VI wherein R¹¹ is chlorine is usedin this reaction, the starting materials are preferably used in aboutstoichiometric amounts, i.e. for one mol of the sulphenyl chloride offormula VI there are preferably used about 2 mol of the carbamoyl oximeof formula I'.

The isolation of the compounds of formula I is carried out usingstandard procedures.

The products prepared according to the above-noted procedures arenormally obtained as a mixture of two or more isomers. The isomers canbe separated by conventional procedures.

The oximes of formula II which are utilized as starting materials inProcedures A, B and C above are novel. They can be prepared bynitrosating a thiazoline or 5,6-dihydro-2H-1,4-thiazine of the formula##STR9## wherein A and R³ are as defined above, conveniently in thepresence of a diluent.

The nitrosation is conveniently effected by conventional procedures,e.g. using a nitrite, e.g. an alkali metal nitrite such as sodiumnitrite, with addition of an acid such as acetic acid, propionic acid, amixture of acetic acid and acetic anhydride, or an aqueous mineral acidsuch as hydrochloric acid. Nitrogen tetroxide, nitrosyl chloride andalkyl nitrites such as methyl nitrite, ethyl nitrite or isopentylnitrite can also be used as the nitrosating compounds. These lattercompounds can be reacted not only in acidic but also in alkaline medium.

Diluents for this reaction include water, alcohols, acetonitrile,aromatic hydrocarbons, chlorinated hydrocarbons as well as ethers.

The reaction is conveniently carried out at temperatures between -20° C.and 100° C., and, preferably, between 0° C. and 60° C.

For the isolation of the compounds of formula II, the solvent can beremoved, e.g. by filtration or distillation, and the residue can eitherbe washed, e.g. with water, dried and crystallized or purifiedchromatographically, or can be taken up in a suitable solvent, washedwith water, the solution dried over a suitable drying agent, e.g.anhydrous sodium sulfate, and, after distilling off the solvent, theproduct can be recrystallized or purified chromatographically.

The thiazolines of formula VII wherein A is a group (a), which areutilized as starting materials, are either known or can be preparedaccording to known methods, e.g. in accordance with F. Asinger et al.,Ann. 610, 17-24 and 33-49 (1957), Angew. Chemie 79, 953 (1967) or DOS 2645 731.

The 5,6-dihydro-2H-1,4-thiazines of formula VII wherein A is the group(b), which are also utilized as starting materials, are likewise partlyknown (e.g. from Ann. 652, 50 (1962) and Asinger et al., Monatsheft furChemie 102, 321-332 (1971)), or can be prepared analogous to knownmethods. The following Process Scheme represents a general preparationprocess: ##STR10## Since the 5,6-dihydro-2H-1,4-thiazines of formulaVII' are very sensitive to autooxidation in air and are convertedthereby into corresponding sulfoxides and sulfones, it is convenient toconvert the 5,6-dihydro-2H-1,4-thiazine compound without isolationdirectly into the corresponding oxime of formula II wherein A signifiesthe group (b) by a one-pot process. The reaction with a nitroso compoundcan be carried out as described above, preferably with the use of analkyl nitrite in alkaline medium.

The oximes of formula II, which are utilized as starting materials inProcedures A, B and C, can also be prepared from glyoxyl hydroxamic acidchloride or an alkyl or cycloalkyl derivative thereof and thecorresponding mercaptoamine of the formula H₂ N--A--SH, according to thefollowing Process Scheme: ##STR11##

the reaction is conveniently effected in an inert diluent, in thepresence of an acid-binding agent and in a temperature range from -30°C. to room temperature. The diluents for this reaction include inertorganic solvents. Preferred solvents are ethers and ether-like compoundssuch as diethyl ether and tetrahydrofuran; pyridine; acetonitrile;alcohols; and water.

Preferred acid-binding agents are alkali carbonates such as sodiumcarbonate, potassium carbonate and sodium bicarbonate, lower alkylaminessuch as triethylamine; and pyridine.

The isocyanates of formula III are either known or can be preparedaccording to known methods, e.g. by reaction of the respective amine R⁵NH₂ with phosgene and subsequent heating. Examples of such knownisocyanates are methyl isocyanate, ethyl isocyanate, isopropylisocyanate, tert.-butyl isocyanate, allyl isocyanate, cyclopropylisocyanate and cyclohexyl isocyanate.

The carbamoyl halides of formula IV are likewise either known or can beprepared according to known methods, e.g. by reaction of the respectiveamine R⁴ R⁵ NH will phosgene. Examples of such known carbamoyl halidesare dimethylcarbamoyl chloride, methylethylcarbamoyl chloride,N-methyl-N-trichloromethylsulphenylcarbamoyl fluoride,N-methyl-N-flurordichloromethylsulphenyl-carbamoyl fluoride,N-methyl-N-chlorodifluoromethylsulphenyl-carbamoyl fluoride,N-methyl-N-(3-trifluoromethylphenylsulphenyl)-carbamoyl fluoride,N-acetyl-N-methylcarbamoyl chloride,N-methyl-N-(4-chlorophenylsulphenyl)-carbamoyl fluoride,N-methyl-N-(morpholin-1-ylsulphenyl)-carbamoyl fluoride andN-methyl-N-(tert.-butylthio)sulphenylcarbamoyl fluoride.

The amines of formula V are likewise either known or can be preparedaccording to known methods. Examples of such known amines aremethylamine, ethylamine, dimethylamine, methylethylamine andallylmethylamine.

The sulphenyl chlorides of formula VI are likewise either known or canbe prepared according to known methods. Examples of such known sulphenylchlorides are methylsulphenyl chloride, trichloromethylsulphenylchloride, dichlorofluoromethylsulphenyl chloride,chlorodifluoromethylsulphenyl chloride, trifluoromethylsulphenylchloride, phenylsulphenyl chloride, 2,4-dichlorophenylsulphenylchloride, 3-trifluoromethylphenylsulphenyl chloride,3-methylphenylsulphenyl chloride,4-chloro-3-trifluoromethylphenylsulphenyl chloride, sulfur dichlorideand sulfur monochloride.

The compounds of this invention are active as pesticides and, inparticular, for the control of insects, mites, nematodes and molluscs.

They are especially valuable against:

(a) Coleoptera such as e.g. Epilachna spp., Leptinotarsa decemlineata,Anthonomus spp., Conotrachelus nenuphar, Lema spp., Lissorhoptrusoryzaephilus, Phyllotreta spp., Psylliodes chrysocephala, Meligethesaenus, Ceutorrhynchus assimilia, Agriotes spp., Otiorhynchus sulcatus,Melolontha melolontha and Diabrotica spp.;

(b) Lepidoptera such as e.g. Laspeyresia spp., Adoxophyes orana, Tortrixviridana, Cheimatobia brumata, Lyonetia clerkella, Operophtera brumata,Lithocolletis blancardella, Porthetria dispar, Mamestra brassicae,Agrotis segetum, Plutella spp., Pieris brassicae, Choristoneurafumiferana, Heliothis spp., Spodoptera spp., Pectinophora gossipiella,Chilo spp., Ostrinia nubilalis, Clysia ambiguella, Lobesia botrana;

(c) Diptera such as e.g. Drosophila melanogaster, Ceratitis spp.,Oscinella frit, Dacus spp. and Rhagoletis spp. Leatherjacket spp.,Sciara spp. Phorbia spp. and Megasetia agarici;

(d) Homoptera, i.e. aphids such as e.g. Aphis fabae, Myzus persicae andfurther species of these genera, Rhophalosiphon spp., Schizaphis spp.,Dysaphis spp., Eriosoma spp., Macrosiphum spp., Adelges spp., Sitobionavenae, Metopolophium spp. as well as shield lice and soft lice such ase.g. Aspidiotus spp., Saissetia spp., Quadraspidiotus perniciosus,Aonidiella aurantii, Coccus spp., Lepidosaphes spp., Planococcus spp.,Pseudocossus spp., Ceroplastes spp., Icerya purchasi, Chrysomphalusspp., Parlatoria spp., Rhizoecus spp. as well as cicades such as e.g.Nephotettix spp., Laodelphax spp., Nilaparvata spp., Sogatella spp. andErythroneura spp.;

(e) Aleurodidae such as e.g. Trialeurodes vaporariorum, Dialeurodesspp., Aleurothrixus spp., Bemisia spp., Aleyrodes spp., moreover speciesof thrips and bugs;

(f) Acarina such as e.g. Tetranychus urticae, Panonychus ulmi and otherTetranychida, Tarsonemida such as Steneotarsonemus spp., Tenuipalpidasuch as Brevipalpus, Eriophyda such as Phyllocoptruta oleivora, Aceriasheldoni, Eriophyes spp., Aceria spp. and further ticks;

(g) Nematoda such as e.g. free-living nematodes (inter alia Pratylenchusspp. such as P. penetrans), leaf-parasitic nematodes (inter aliaAphelenchoides) and root-parasitic nematodes (inter alia Meloidogynnaespp. such as M incognita, Globodera spp. such as G. rostochiensis); and

(h) Mollucsa such as e.g. Deroceras spp.

The compounds of this invention are systemically active and act ascontact poisons and feed poisons.

The instant invention is also directed to pesticidal compositions suchas solutions, emulsions, suspension, powders, pastes and granulateswhich contain inert carrier materials and, as the active ingredient, oneor more of the compounds of formula I.

These compositions are prepared by known methods such as, for example,by mixing the active substance with extenders (liquid solvents,liquified gases under pressure and/or solid carrier substances) and, ifdesired, surface-active agents (emulsifiers, wetting agents ordispersing agents). When water is used as the extender, organic solventscan also be used as auxilliary solvents.

Examples of liquid solvents include: aromatics such as xylene, tolueneand alkyl-naphthalenes; chlorinated aromatics and chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes and methylenechloride; aliphatic hydrocarbons such as cyclohexane and paraffins(e.g., petroleum fractions); alcohols such as butanol and glycol as wellas their ethers and esters; ketones such as acetone, methyl ethylketone, methyl isobutyl ketone and cyclohexanone; strongly polarsolvents such as dimethylformamide, N-methylpyrrolidone anddimethylsulfoxide, and water.

Examples of liquified gaseous extenders or carrier substances includeliquids which are gaseous at normal temperature and under normalpressure such as aerosol propellants, e.g. halogenated hydrocarbons(e.g. dichlorodifluoromethane).

Examples of solid carrier substances include natural mineral powderssuch as kaolins, clays, talc, chalk, quartz, attapulgite,montmorillonite and diatomaceous earth, and synthetic mineral powderssuch as high-dispersible silicic acid, aluminum oxide and silicates.

Surface-active agents, especially emulsifying agents and wetting agents,suitable for use in the pesticidal compositions of this invention can benon-ionic or anionic. Examples of non-ionic emulsifiers which can beused include polyoxyethylene-fatty acid esters, polyoxyethylene-fattyalcohol ethers and alkylaryl-polyglycol ethers. Examples of anionicemulsifers include alkyl sulfonates, alkyl sulfates and aryl sulfonates.

Examples of dispersing agents include lignin, sulfite lyes and methylcellulose.

The active ingredients of this invention can be present in thecomposition in admixture with other known active substances. Thecompositions generally contain between 0.0005 wt. % and 95 wt. % oftotal active substances, preferably between 1 wt. % and 75 wt. %.

The pesticidal compositions of the present invention can be inapplication forms suitable for storage or shipment. In such forms theconcentration of active ingredients is normally at the higher end of theabove concentration range. These forms can then be diluted with the sameor different carrier materials to afford active ingredientconcentrations suitable for practical use, and such concentrationsnormally lie at the lower end of the above-noted concentration range.

The active ingredients can also be used as such in the compositions orin application forms prepared from these compositions such asready-for-use solutions, emulsions, foams, suspensions, powders, pastes,soluble powders, dusting agents and granulates. They are used in theusual procedures such as squirting, spraying, smoke-screening, dusting,scattering, drilling-in, vaporizing, pouring, drenching or incrustating.

The concentrations of active ingredient in the ready-for-usepreparations can vary over wide limits. In spray liquors, theconcentration lies between 0.0005 wt. % and 20 wt. %.

The active ingredients can also be used with good effect in theultra-low-volume process (ULV) where it is possible to formulate sprayliquors having preferably from 10 to 20 wt. %.

The active ingredients can also be used with good effect in thelow-volume process and in the high-volume process where it is possibleto formulate spray liquors having from 0.5 to 1.0 or 0.05 to 0.1 wt. %of active ingredient respectively.

In granulates, the concentration of active ingredients is preferablyfrom 2 to 10 wt. %.

The pesticidal compositions of the present invention can contain otheractive substances, for example, other pesticides, besides the compoundsof formula I. Such combination compositions are suitable for increasingthe activity or for broadening the spectrum of activity.

In preparing the pesticidal compositions of the present invention, theactive ingredient of formula I is mixed with inert carrier material. Inthe case of pulverous compositions the active ingredient can be mixedwith the carrier substances, for example, by grinding together; or theinert carrier material can be impregnated with a solution or suspensionof the active ingredient and then the solvent or suspension agent can beremoved by evaporation, heating or by sucking-off under reducedpressure. By the addition of wetting and/or dispersing agents suchpulverous compositions can be made readily wettable with water so thatthey can be converted into aqueous suspensions which are suitable asspray compositions. For the manufacture of emulsifiable concentrates,which are especially suitable for storage and shipment, the activeingredient can be mixed, for example, with an emulsifying agent ordissolved in an inert solvent and thereafter mixed with an emulsifier.Ready-for-use emulsions are prepared by diluting such concentrates withwater.

The pesticidal compositions of the present invention are used bytreating the locus to be protected or the pests themselves with thepesticidal compositions of the present invention. This method of use ispreferably carried out by applying the composition to the soil orleaves, depending on the pests to be controlled.

The following Examples serve for the more precise illustration of theinvention.

EXAMPLE 1

20.0 g (0.126 mol) of 5-oxo-2,2,4-trimethyl-3-thiazoline oxime aredissolved in 100 ml of chloroform. To the solution are added 15 ml(0.252 mol) of freshly distilled methyl isocyanate as well as 3 drops oftriethylamine. The mixture, which warms slightly after a short time, isleft to stand at room temperature for 16 hours. Subsequently, theslightly turbid solution is filtered, and the solvent and excess methylisocyanate are distilled off in vacuo. The oily residue is purifiedchromatographically on 250 g of silica gel using ethyl acetate/n-hexane(1:1) for the elution. The solvent is removed by evaporation, and theresulting residue is recrystallized from methylenechloride/n-hexane/diethyl ether to yield5-oxo-2,2,4-trimethyl-3-thiazoline O-(methylcarbamoyl) oxime as whitecrystals, m.p. 90°-92° C.

EXAMPLE 2

3.0 g (0.019 mol) of 5-oxo-2,2,4-trimethyl-3-thiazoline oxime are addedportionwise to a suspension of 0.9 g of sodium hydride in 20 ml oftetrahydrofuran. The sodium hydride was liberated shortly before its usefrom a 55% suspension in oil by two-fold extraction with a small amountof absolute pentane. After completion of the hydrogen evolution, themixture is stirred at room temperature for an additional 1 hour. 2.05 g(0.019 mol) of dimethylcarbamoyl chloride are added dropwise, and thereaction mixture is stirred at room temperature for 16 hours. Theresidue is then taken up in diethyl ether, and the organic phase iswashed with saturated sodium chloride solution and dried over anhydroussodium sulfate. The solvent is subsequently distilled off, and theresidue is recrystallized from diethyl ether/n-hexane to yield5-oxo-2,2,4-trimethyl-3-thiazoline O-(dimethylcarbamoyl) oxime, m.p.92°-95° C.

EXAMPLES 3-22

Compounds of formula I are prepared from appropriate starting materialsof formula II and III according to the procedure described in Example 1.The compounds of formula I are listed in the following Table A.

                                      TABLE A                                     __________________________________________________________________________     ##STR12##                                                                    Example                                                                            A          R.sup.3                                                                              R.sup.5  M.p.                                          __________________________________________________________________________          ##STR13## CH.sub.3                                                                             CH.sub.3 -- (oil)                                      4                                                                                   ##STR14## CH.sub.3                                                                             CH.sub.3 -- (oil)                                      5                                                                                   ##STR15## CH.sub.3                                                                             CH.sub.3 117-119° C.                            6                                                                                   ##STR16## CH.sub.3                                                                             CH.sub.3 112-114° C.                            7                                                                                   ##STR17## CH.sub.3                                                                             CH.sub.3 109-110° C.                            8                                                                                   ##STR18## CH.sub.3                                                                             CH.sub.3 120-123° C.                            9                                                                                   ##STR19## H      CH.sub.3 95-96° C.                              10                                                                                  ##STR20## C.sub.2 H.sub.5                                                                      CH.sub.3 102-105° C.                            11                                                                                  ##STR21## (CH.sub.3).sub.2 CH                                                                  CH.sub.3 94-96° C.                              12                                                                                  ##STR22## CH.sub.3                                                                             C.sub.2 H.sub.5                                                                        95-97° C.                              13                                                                                  ##STR23## CH.sub.3                                                                             (CH.sub.3).sub.2 CH                                                                    80-81° C.                              14   CH.sub.2 CH.sub.2                                                                        CH.sub.3                                                                             CH.sub.3 143.5° C.                                                              (with decom-                                                                  position)                                     15   CH.sub.2 CH.sub.2                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3 108-110° C.                            16   CH.sub.2 CH.sub.2                                                                        (CH.sub.3).sub.2 CH                                                                  CH.sub.3 79-80.5° C.                            17   CH.sub.2 CH.sub.2                                                                         ##STR24##                                                                           CH.sub.3 109-111° C.                            18                                                                                  ##STR25##                                                                                ##STR26##                                                                           CH.sub.3 161-163° C.                            19                                                                                  ##STR27## CH.sub.3                                                                             CH.sub.3 77-79° C.                              20                                                                                  ##STR28## CH.sub.3                                                                             CH.sub.2 CHCH.sub.2                                                                    46-48° C.                              21                                                                                  ##STR29## CH.sub.3                                                                              ##STR30##                                                                             77-78° C.                              22                                                                                  ##STR31## CH.sub.3                                                                             CH.sub.3 48-50° C.                              __________________________________________________________________________

EXAMPLE 23

2-Oxo-5,6-dihydro-3-methyl-2H-1,4-thiazine oxime is reacted withdimethylcarbamoyl chloride as described in Example 2 to yield2-oxo-5,6-dihydro-3-methyl-2H-1,4-thiazine O-(dimethylcarbamoyl) oxime,m.p. 64°-65° C.

EXAMPLE 24

3.2 g (0.015 mol) of 5-oxo-2,2,4-trimethyl-3-thiazolineO-(methylcarbamoyl) oxime are dissolved in 15 ml of absolute chlorideand treated dropwise at 0° C. with stirring with 1.2 ml of pyridine and0.55 ml (0.086 mol) of freshly distilled sulfur dichloride. The mixtureis allowed to come to room temperature slowly and then stirred for 16hours. The mixture is diluted with 100 ml of methylene chloride, washedonce with dilute hydrochloric acid and twice with semi-saturated sodiumchloride solution and dried over anhydrous sodium sulfate. After thesolvent is distilled off, the oily residue is purified by means oftwo-fold chromatography on silica gel (eluent 7% acetone in chloroform;40% toluene in ethyl acetate). Recrystallizations from acetone/n-hexaneyield N,N'-bis-[2,24-trimethyl-3-thiazolin-5-O-(methylcarbamoyl)oximino]sulfide, m.p.152°-154° C.

EXAMPLE 25

3.0 g (0.019 mol) of 5-oxo-2,2,4-trimethyl-3-thiazoline oxime aresuspended in 10 ml of absolute acetonitrile. To the suspension at 0° C.there are successively added 5.5 g of anhydrous potassium carbonate and,dropwise, a solution of 4.52 g ofN-(di-n-butylaminosulphenyl)-N-methylcarbamoyl fluoride in 10 ml ofabsolute acetonitrile. The reaction mixture is allowed to stir well atroom temperature for 20 hours. Subsequently, the precipitated potassiumsalt is filtered off, and the filtrate is evaporated. Chromatography ofthe crude oily product on silica gel with ethyl acetate/toluene (1:3) asthe eluent yields 5-oxo-2,2,4-trimethyl-3-thiazolineO-[N-(di-n-butylaminosulphenyl)-N-methylcarbamoyl]oxime, n_(D) ²⁰1.5200.

EXAMPLES 26-30

In a manner analogous to the method described in Example 25,5-oxo-2,2,4-trimethyl-3-thiazoline oxime and the appropriate startingmaterial of formula IV are reacted to produce the compounds of theformula I given in the following Table B.

                  TABLE B                                                         ______________________________________                                         ##STR32##                                                                    Example  R.sup.5         M.p.      n.sub.D.sup.20                             ______________________________________                                        26                                                                                      ##STR33##      103-104° C.                                                                      --                                         27       SSCH(CH.sub.3).sub.2                                                                          --        1.5590                                     28       SSC(CH.sub.3).sub.3                                                                           74-76° C.                                                                        --                                         29       SCCl.sub.3      90-93° C.                                                                        --                                         30                                                                                      ##STR34##      144-146° C.                                                                      --                                         ______________________________________                                    

EXAMPLE 31

2-Oxo-5,6-dihydro-3-isopropyl-2H-1,4-thiazine oxime is reacted withN-methyl-N-morpholinosulphenylcarbamoyl fluoride as described in Example25 to yield 2-oxo-5,6-dihydro-3-isopropyl-2H-1,4-thiazineO-(N-methyl-N-morpholinosulphenylcarbamoyl)oxime, m.p. 127°-128.5° C.

EXAMPLE 32

8.3 ml of triethylamine are added dropwise to a suspension of 8.59 g of5-oxo-2,2,4-thimethyl-3-thiazoline oxime in a solution of 10.0 g ofbis-(N-methyl-N-flurorocarbonylamino)sulfide in 100 ml of absolutetoluene, cooled to -50° C. The resulting clear solution is allowed towarm slowly to 0° C. during 11/2 hours, during which time a crystallineproduct is precipitated. The reaction mixture is poured into ice-coldbrine and extracted with ethyl acetate. After drying the organic phaseover anhydrous sodium sulfate and evaporating it, the resulting residueis purified by chromatography on silica gel (eluent: ethylacetate/n-hexane 1:1). Crystallization from ethyl acetate/n-hexaneyields 5-oxo-2,2,4-trimethyl-3-thiazolineO-[N-(N-methylfluoroformamidothio)-N-methylcarbamoyl]oxime, m.p. 77°-79°C.

1.13 g of the product of the previous stage and 0.61 g of2-oxo-5,6-dihydro-3-isopropyl-2H-1,4-thiazine oxime are suspended in 25ml of absolute toluene at 0° C. The suspension is treated with 0.57 g oftriethylamine, and the reaction mixture is stirred and slowly warmed toroom temperature during 16 hours. The mixture is worked up as describedfor the previous stage. Crystallization from ethyl acetate/n-hexaneyields the O,O'-[thiobis(methyliminocarbonyl)]dioxime of5-oxo-2,2,4-trimethyl-3-thiazoline and2-oxo-5,6-dihydro-3-isopropyl-2H-1,4-thiazine, m.p. 141.5°-143.5° C.

PREPARATION OF THE STARTING MATERIALS EXAMPLE 33

The 5-oxo-2,2,4-trimethyl-3-thiazoline oxime required as the startingmaterial in Examples 1, 2, 12, 20, 21, 25-30 and 32 is prepared asfollows.

32.0 g (0.46 mol) of sodium nitrite are suspended in a solution of 30.0g (0.232 mol) of 2,2,4-trimethyl-3-thiazoline dissolved in 200 ml ofacetonitrile. Then, there are added dropwise to the suspension, cooledto -10° C., with stirring 26.6 ml (0.464 mol) of acetic acid andsubsequently 21.9 ml (0.232 mol) of acetic anhydride. After completionof the addition, the reaction mixture is warmed to 0° C. and stirred atroom temperature for an additional 3 hours.

The reaction mixture is then partially concentrated in vacuo, theresidue is treated with about 500 ml of water and sufficient solidsodium bicarbonate is added to the mixture to afford pH 6. Afterthree-fold extraction with 200 ml of chloroform each time, the extractsare washed with water, the organic phase is dried over anhydrous sodiumsulfate, and the phase is concentrated in vacuo until it is turbid. Theorganic phases is filtered, and the filtrate is treated with n-hexane.5-oxo-2,2,4-trimethyl-3-thiazoline oxime precipitates as light browncrystals and is filtered off. Two recrystallizations fromchloroform/n-hexane yield a product which melts at 161°-163° C.

EXAMPLE 34

The 5-oxo-2,2,4-trimethyl-3-thiazoline oxime can also be prepared asfollows.

30.0 g (0.232 mol) of 2,2,4-trimethyl-3-thiazoline and 17.6 g (0.255mol) of sodium nitrite are dissolved in 75 ml of water and 26.6 ml(0.464 mol) of acetic acid are added dropwise, with stirring at 45° C.The internal temperature of the reaction mixture is allowed to riseslowly to 10°-15° C., and the mixture is then stirred at thistemperature for an additional 2 hours. The product precipitates asochre-brown crystals and is filtered, washed with water and dried invacuo. A single recrystallization from chloroform/n-hexane yields5-oxo-2,2,4-trimethyl-3-thiazoline oxime, m.p. 159°-161° C.

EXAMPLES 35-46

The corresponding substituted 3-thiazolines are reacted with sodiumnitrite analogous to the process described in Example 33 or 34 in orderto prepare the starting materials of formula II listed in the followingTable C. The corresponding end products of formula I are also given inthis Table.

                  TABLE C                                                         ______________________________________                                         ##STR35##                                                                                                          Example No.                             Ex-                                   of the end-                             am-                                   product of                              ple  R.sup.1                                                                              R.sup.2   R.sup.3 M.p.    formula I                               ______________________________________                                        35   CH.sub.3                                                                             C.sub.2 H.sub.5                                                                         CH.sub.3                                                                              --      3, 13                                                                 (not puri-                                                                    fied)                                           36   C.sub.2 H.sub.5                                                                      n-C.sub.4 H.sub.9                                                                       CH.sub.3                                                                              -- (oil)                                                                              4                                       37   (CH.sub.2).sub.4                                                                           CH.sub.3  157-159° C.                                                                    5                                         38   H      CH.sub.3  CH.sub.3                                                                              145-148° C.                                                                    6                                       39   H      C.sub.2 H.sub.5                                                                         CH.sub.3                                                                              115-118° C.                                                                    7                                       40   H      (CH.sub.3).sub.2 CH                                                                     CH.sub.3                                                                              --      8                                                                     (not puri-                                                                    fied)                                           41   CH.sub.3                                                                             C.sub.2 H.sub.5                                                                         H       --      9                                                                     (not puri-                                                                    fied)                                           42   CH.sub.3                                                                             CH.sub.3  C.sub.2 H.sub.5                                                                       --      10                                                                    (not puri-                                                                    fied)                                           43   CH.sub.3                                                                             CH.sub.3  (CH.sub.3).sub.2 CH                                                                   187-192° C.                                                                    11                                      44   CH.sub.3                                                                             CH.sub.3                                                                                 ##STR36##                                                                            180- 181.5° C.                                                                 18                                      45   CH.sub.3                                                                              ##STR37##                                                                              CH.sub.3                                                                              -- (not puri- fied)                                                                   19                                      46   C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         CH.sub.3                                                                              --      22                                                                    (not puri-                                                                    fied)                                           ______________________________________                                    

EXAMPLE 47

The 2-oxo-5,6-dihydro-3-isopropyl-2H-1,4-thiazine oxime required as thestarting material in Examples 16, 31 and 32 is prepared as follows.

18.4 g (0.80 mol) of sodium are dissolved in 400 ml of absolutemethanol. Dry cysteamine is added portionwise to the solution with theexclusion of air, and the mixture is stirred until a clear solution isobtained. The reaction mixture is warmed briefly at 55° C. Subsequently,132 g (0.80 mol) of 1-bromo-3-methyl-2-butanone are added dropwisethereto while the internal temperature is held at 30° C. by cooling withice water. The reaction mixture is stirred at room temperature for anadditional 30 minutes.

Then, a solution of 18.4 g (0.80 mol) of sodium in 400 ml of methanol isadded to the reaction mixture, and, after 10 minutes, the mixture istreated dropwise with 106.4 ml (0.80 mol) of isopentyl nitrite. Theinternal temperature of the reaction mixture thereby rises to 56° C.within 50 minutes. The mixture is allowed to stir at room temperaturefor 16 hours and is then treated with 2.3 liters of water. The aqueousmixture is filtered through Celite, and the clear filtrate is treated,with stirring and cooling, with 45.6 ml (0.80 mol) of acetic acid toobtain pH 6. After 30 minutes, the precipitated crystals are filteredoff, washed with a large amount of water and subsequently with coldisopropanol, and dried to yield2-oxo-5,6-dihydro-3-isopropyl-2H-1,4-thiazine oxime as crystals, m.p.167°-169° C.

EXAMPLES 48-50

The starting materials of formula II listed in the following Table D areprepared from corresponding starting materials analogously to theprocess described in Example 47. The corresponding end products offormula I are also listed in this Table.

                  TABLE D                                                         ______________________________________                                         ##STR38##                                                                                                   Example No. of                                                                the end product                                Example   R.sup.3  M.p.        of formula I                                   ______________________________________                                        48        CH.sub.3 197° C. (with                                                                      14, 23                                                            decomposition)                                             49        C.sub.2 H.sub.5                                                                        155-157° C.                                                                        15                                             50                                                                                       ##STR39##                                                                             155-157° C.                                                                        17                                             ______________________________________                                    

EXAMPLE 51

The 2-oxo-5,6-dihydro-3-methyl-2H-1,4-thiazine oxime required as thestarting material in Examples 14 and 23 can also be manufactured asfollows.

2.27 g (0.02 mol) of cysteamine hydrochloride are suspended in 40 ml ofabsolute tetrahydrofuran and treated with 5.55 ml (0.04 mol) oftriethylamine to free the base. The mixture is stirred for 15 minutes atroom temperature and then cooled down to about -30° C. At thistemperature a solution of 2.42 g (0.02 mol) of pyruvyl chloride 1-oximein 10 ml of absolute tetrahydrofuran is added dropwise. The reactionmixture is allowed to warm to room temperature while being well stirred.After two hours ice-water and then dilute hydrochloric acid are addeduntil a pH of 5-6 has been attained. The reaction mixture is extractedtwice with ethyl acetate and the organic phase is washed with sodiumchloride solution, dried over anhydrous sodium sulfate and finallyevaporated. The resulting crystalline residue is treated with activecharcoal. After recrystallization from hot ethyl acetate and n-hexanethere is obtained pure 2-oxo-5,6-dihydro-3-methyl-2H-1,4-thiazine oxime,m.p. 197° C. (with decomposition).

EXAMPLE 52

This example illustrates compositions containing a compound of formula Ias the active ingredient:

    ______________________________________                                                                 g/liter                                              ______________________________________                                        (a) Active Ingredient, a compound of formula I                                                               250                                                N--Methyl-2-pyrrolidone    500                                                Emulsifier mixture consisting of:                                             Calcium alkylarylsulfonate, alkylphenol                                                                  50                                                 ethoxylate, block polymerisate of pro-                                        pylene oxide and ethylene oxide                                               Calcium dodecylbenzene sulfonate                                                                         25                                                 Solvent (mixture of mono-, di- and tri-lower                                                             ad 1000 ml                                         alkylbenzenes)                                                            (b) Active Ingredient, a compound of formula I                                                               500                                                N--Methyl-2-pyrrolidone    ad 1000 ml                                     (c) Active Ingredient, a compound of formula I                                                               50      g                                          High-dispersible silicic acid                                                                            5       g                                          Sodium lauryl sulfate      1       g                                          Sodium lignosulfonate      2       g                                          Kaolin                     42      g                                                                     100     g                                      ______________________________________                                    

We claim:
 1. A compound of the formula ##STR40## wherein A is a group(a) ##STR41## R¹ and R² are hydrogen, lower alkyl or cycloalkylcontaining 3 to 6 carbon atoms, or together with the carbon atom towhich they are attached a 4- to 8-membered, saturated hydrocarbonring,R³ is hydrogen, lower alkyl or cycloalkyl containing 3 to 6 carbonatoms, R⁴ is hydrogenand R⁵ is lower alkyl, lower alkenyl or cycloalkylcontaining 3 to 6 carbon atoms,or R⁴ is lower alkyland R⁵ is loweralkyl, lower alkylcarbonyl, tri(lower alkyl)silyl or a group (c)

    --S.sub.m --R.sup.6                                        (c)

R⁶ is alkyl; lower haloalkyl, phenyl, phenyl substituted with halogen,lower alkyl and/or trifluoromethyl; or a group (d) or (e)

    --NR.sup.7 R.sup.8                                         (d) ##STR42## R.sup.7 and R.sup.8 are lower alkyl or lower haloalkyl, or together with the nitrogen atom to which they are attached a piperidino or morpholino group,

R⁹ is lower alkyland m is 1 or
 2. 2. A compound according to claim 1,wherein R¹ in the group (a) is hydrogen or lower alkyl.
 3. A compoundaccording to claim 2, wherein R² in the group (a) is hydrogen or loweralkyl.
 4. A compound according to any one of claims 1, 2 or 3, wherein Ais a group (a) and R³ is methyl.
 5. A compound according to any one ofclaims 1, 2 or 3, wherein R⁴ is hydrogen and R⁵ is lower alkyl.
 6. Acompound according to claim 1, 5-oxo-2,2,4-trimethyl-3-thiazolineO-(methylcarbamoyl) oxime.
 7. A compound according to claim 1,5-oxo-2,2,4-trimethyl-3-thiazoline O-(dimethylcarbamoyl) oxime.
 8. Acompound according to claim 1, 5-oxo-2-ethyl-2,4-dimethyl-3-thiazolineO-(methylcarbamoyl) oxime.
 9. A compound according to claim 1,5-oxo-2-ethyl-2-(n-butyl)-4-methyl-3-thiazoline O-(methylcarbamoyl)oxime.
 10. A compound according to claim 1,5-oxo-2,2-tetramethylene-4-methyl-3-thiazoline O-(methylcarbamoyl)oxime.
 11. A compound according to claim 1,5-oxo-2,4-dimethyl-3-thiazoline O-(methylcarbamoyl) oxime.
 12. Acompound according to claim 1, 5-oxo-2-ethyl-4-methyl-3-thiazolineO-(methylcarbamoyl) oxime.
 13. A compound according to claim 1,5-oxo-2-isopropyl-4-methyl-3-thiazoline O-(methylcarbamoyl) oxime.
 14. Acompound according to claim 1, 5-oxo-2-ethyl-2-methyl-3-thiazolineO-(methylcarbamoyl) oxime.
 15. A compound according to claim 1,5-oxo-2,2-dimethyl-4-ethyl-3-thiazoline O-(methylcarbamoyl) oxime.
 16. Acompound according to claim 1,5-oxo-2,2-dimethyl-4-isopropyl-3-thiazoline O-(methylcarbamoyl) oxime.17. A compound according to claim 1, 5-oxo-2,2,4-trimethyl-3-thiazolineO-(ethylcarbamoyl) oxime.
 18. A compound according to claim 1,5-oxo-2-ethyl-2,4-dimethyl-3-thiazoline O-(isopropylcarbamoyl) oxime.19. A compound according to claim 1,5-oxo-2,2-dimethyl-4-cyclopropyl-3-thiazoline O-(methylcarbamoyl) oxime.20. A compound according to claim 1,5-oxo-2-cyclopropyl-2,4-dimethyl-3-thiazoline O-(methylcarbamoyl) oxime.21. A compound according to claim 1,N,N'-bis-[2,2,4-trimethyl-3-thiazoline-5-O-methylcarbamoyl)oximino]sulfide22. A compound according to claim 1, 5-oxo-2,2,4-trimethyl-3-thiazolineO-[N-(di-n-butylaminosulphenyl)-N-methylcarbamoyl]oxime.
 23. A compoundaccording to claim 1, 5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-methyl-N-morpholinosulphenylcarbamoyl) oxime.
 24. A compoundaccording to claim 1, 5-oxo-2,2,4-trimethyl-3-thiazolineO-(allylcarbamoyl) oxime.
 25. A compound according to claim 1,5-oxo-2,2,4-trimethyl-3-thiazoline O-(cyclopropylcarbamoyl) oxime.
 26. Acompound according to claim 1, 5-oxo-2,2-diethyl-4-methyl-3-thiazolineO-(methylcarbamoyl) oxime.
 27. A compound according to claim 1,5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-isopropylthiosulphenyl-N-methylcarbamoyl) oxime.
 28. A compoundaccording to claim 1, 5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-tert.butylthiosulphenyl-N-methylcarbamoyl) oxime.
 29. A compoundaccording to claim 1, 5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-trichloromethylsulphenyl-N-methylcarbamoyl) oxime.
 30. A compoundaccording to claim 1, 5-oxo-2,2,4-trimethyl-3-thiazolineO-(N-[(4-chlorophenyl)sulphenyl]-N-methylcarbamoyl) oxime.
 31. Apesticidal composition which comprises an inert carrier material and, asthe active ingredient, an amount which is effective as a pesticide of atleast one compound of the formula ##STR43## wherein A is a group (a)##STR44## R¹ and R² are hydrogen, lower alkyl or cycloalkyl containing 3to 6 carbon atoms, or together with the carbon atom to which they areattached a 4- to 6-membered, saturated hydrocarbon ring,R³ is hydrogen,lower alkyl or cycloalkyl containing 3 to 6 carbon atoms, R⁴ ishydrogenand R⁵ is lower alkyl, lower alkenyl or cycloalkyl containing 3to 6 carbon atoms,or R⁴ is lower alkyland R⁵ is lower alkyl, loweralkylcarbonyl, tri(lower alkyl)silyl or a group (c)

    --S.sub.m --R.sup.6                                        (c)

R⁶ is alkyl; lower haloalkyl; phenyl, phenyl substituted with halogen,lower alkyl and/or trifluoromethyl; or a group (d) or (e)

    --NR.sup.7 R.sup.8                                         (d) ##STR45## R.sup.7 and R.sup.8 signify lower alkyl or lower haloalkyl, or together with the nitrogen atom to which they are attached a piperidino or morpholino group, R.sup.9 is lower alkyl

and m is 1 or
 2. 32. The pesticidal composition of claim 31 wherein theactive ingredient is 5-oxo-2,2,4-trimethyl-3-thiazolineO-(methylcarbamoyl) oxime.
 33. A method for the control of pests whichcomprises applying to the locus to be so treated or the pests an amountof the pesticidal composition of claim 31 which is effective in thecontrol of pests.
 34. The method of claim 33, wherein the activeingredient of the pesticidal composition is5-oxo-2,2,4-trimethyl-3-thiazoline O-(methylcarbamoyl) oxime.